Addition of E–H (E = N, P, C, O, S) Bonds to Heterocumulenes Catalyzed by Benzimidazolin-2-iminato Actinide Complexes

Abstract

The synthesis and characterization of benzimidazolin-2-iminato actinide(IV) complexes [(BimR1/R2N)An(N{SiMe3}2)3] (An = U, Th) (1–6) is reported. All complexes were obtained in high yields, and their solid state structures were established through single-crystal X-ray diffraction analysis. Using 1–6 as precatalysts, the addition of mono- and bifunctional E–H (E = N, P, C, O, S) substrates to various heterocumulenes, including carbodiimides, isocyanates, and isothiocyanates, was investigated, affording the respective addition products in high yields under very mild reaction conditions. Various amines were applicable to this reaction, indicating a large scope capability of amine nucleophiles for the insertion process.